Composition for semiconductor processing and processing method

This application claims the priority benefit of Japan application serial no. 2022-167493, filed on Oct. 19, 2022. The entirety of the above-mentioned patent application is hereby incorporated by reference herein and made a part of this specification.

The disclosure relates to a composition for semiconductor processing and a processing method using the same.

A semiconductor element is manufactured by forming a fine electronic circuit pattern on a substrate using a photolithography technique. For example, a semiconductor element is manufactured by performing a photolithography step of forming a resist film on a laminate including a metal layer, which serves as a wiring material, an etching-stop layer, an interlayer insulating film and the like on a substrate and exposing and subsequently developing the resist film in a pattern shape to form a pattern and a dry etching step in which plasma etching and plasma ashing are combined. After the photolithography step, there is a need to remove the resist film formed on the laminate. In addition, after the dry etching step, there is a need to remove a residue attached after the processing.

As a technique for removing the resist film after the photolithography step, there has been a proposal of a method in which a composition containing an organic solvent as a main component is used (for example, refer to Patent Document 1: Japanese Patent Laid-Open No. 2007-328338). In addition, as a technique for removing the residue after the dry etching step, there has been a proposal of a method in which a cleaning composition containing hydroxylamine is used (for example, refer to Patent Document 2: Japanese Patent Laid-Open No. 2012-033774).

In such methods, it is usual that the compositions are heated to 50° C. to 65° C. immediately before use and used in order to efficiently remove the resist film or the residue. On the other hand, at the time of commercial manufacturing, these compositions are stored at near room temperature in many cases. However, usually, a composition for semiconductor processing contains a plurality of chemical substances having different properties, and components in the composition for semiconductor processing are likely to alter due to a reaction caused by heating or long-term storage. Therefore, it is difficult to maintain the processing characteristics of the composition for semiconductor processing, and there has been a need to further improve the storage stability of the composition for semiconductor processing in order to improve the manufacturing yield of semiconductor elements.

Several aspects according to the disclosure provide a composition for semiconductor processing capable of maintaining favorable processing characteristics even after being stored for a predetermined period and, furthermore, capable of improving the manufacturing yield of semiconductor elements and a processing method using the same to improve the storage stability.

An aspect of a composition for semiconductor processing according to the present disclosure contains

An aspect of a processing method according to the disclosure includes

An aspect of a processing method according to the disclosure includes

An aspect of a composition for semiconductor processing according to the present disclosure contains

In an aspect of the composition for semiconductor processing,

In an aspect of the composition for semiconductor processing,

In an aspect of the composition for semiconductor processing,

In an aspect of the composition for semiconductor processing,

An aspect of a processing method according to the disclosure includes

An aspect of a processing method according to the disclosure includes

According to the composition for semiconductor processing according to the disclosure, since the storage stability improves, it is possible to maintain favorable processing characteristics even after the composition is stored for a predetermined period and, furthermore, to improve the manufacturing yield of semiconductor elements.

Hereinafter, a preferable embodiment of the disclosure will be described in detail. The disclosure is not limited to the embodiment described below and also includes a variety of modification examples performed within the scope of the gist of the disclosure.

A composition for semiconductor processing according to an embodiment of the disclosure contains (A) a compound represented by the following general formula (1) (in the present specification, also referred to as “(A) component”), (B) a compound represented by the following general formula (2) (in the present specification, also referred to as “(B) component”), (C) a compound having at least one functional group selected from the group consisting of an amino group and a salt thereof (excluding a compound having a carboxyl group and a nitrogen-containing heterocyclic compound) (in the present specification, also referred to as “(C) component”) and (D) a liquid medium (in the present specification, also referred to as “(D) component”), and, when the content of the (A) component is indicated by M[mass %] and the content of the (B) component is indicated by M[mass %], M/Mis 1.0×10to 1.0×10.RO(CH)OP(CH)OH  (1)ROH  (2)

The composition for semiconductor processing according to the present embodiment may be a concentrated type intended to be used after being diluted with a liquid medium such as pure water or an organic solvent or may be an undiluted type intended to be used as it is without being diluted. In the present specification, in the case of being not specified as a concentrated type or an undiluted type, the term “composition for semiconductor processing” is interpreted as a concept including both of the concentrated type and the undiluted type.

In addition, the composition for semiconductor processing according to the present embodiment can be used as a processing agent such as a cleaning agent for removing a particle, a metal impurity or the like present on the surface of an object to be processed after the end of a chemical mechanical polishing (hereinafter, also referred to as “CMP”) step, a resist removal agent for removing a resist film from a semiconductor substrate processed using a resist, a cleaning agent for removing a residue after a dry etching step or an etching agent for removing surface contamination by shallowly etching the surface of a metal wiring or the like.

That is, “processing agent” in the present specification refers to a liquid agent that is an agent prepared by diluting the concentrated type composition for semiconductor processing by adding a liquid medium thereto or the undiluted type composition for semiconductor processing itself and is actually used at the time of processing a surface to be processed. In the concentrated type composition for semiconductor processing, normally, each component is present in a concentrated state. Therefore, each user is able to prepare a processing agent by diluting the concentrated type composition for semiconductor processing with a liquid medium or use the undiluted type composition for semiconductor processing as a processing agent as it is and use the processing agent as a cleaning agent for cleaning the surface of an object to be processed after the end of a CMP step, a resist removal agent, a cleaning agent for residue removal or an etching agent. Hereinafter, each component that is contained in the composition for semiconductor processing according to the present embodiment will be described in detail.

1.1 (A) Component

The composition for semiconductor processing according to the present embodiment contains (A) a compound represented by the following general formula (1).RO(CH)OP(CH)OH  (1)

In the formula (1), R represents a hydrocarbon group and is preferably a hydrocarbon group having 1 to 18 carbon atoms. Examples of the hydrocarbon group having 1 to 18 carbon atoms include an aliphatic saturated hydrocarbon group having 1 to 18 carbon atoms, a cyclic saturated hydrocarbon group having 1 to 18 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms, and, among these, an aliphatic saturated hydrocarbon group having 1 to 18 carbon atoms is preferable.

R in the general formula (1) is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms, still more preferably an alkyl group having 1 to 8 carbon atoms and particularly preferably an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, an isobutyl group and a tert-butyl group, a methyl group, an ethyl group, a n-propyl group and a n-butyl group are preferable, and a n-butyl group is more preferable.

The lower limit value of the content of the (A) component is preferably 40 mass %, more preferably 50 mass % and particularly preferably 55 mass % when the total mass of the composition for semiconductor processing is set to 100 mass %. On the other hand, the upper limit value of the content of the (A) component is preferably 90 mass %, more preferably 85 mass % and particularly preferably 80 mass % when the total mass of the composition for semiconductor processing is set to 100 mass %. When the content of the (A) component is within the above-described range, it is possible to exhibit favorable processing characteristics and, furthermore, to maintain favorable processing characteristics even after the composition is stored for a predetermined period.

1.2. (B) Component

The composition for semiconductor processing according to the present embodiment contains (B) a compound represented by the following general formula (2).ROH  (2)

R in the general formula (2) needs to be the same group as R in the general formula (1). In the general formula (2), R represents a hydrocarbon group and is preferably a hydrocarbon group having 1 to 18 carbon atoms. Examples of the hydrocarbon group having 1 to 18 carbon atoms include an aliphatic saturated hydrocarbon group having 1 to 18 carbon atoms, a cyclic saturated hydrocarbon group having 1 to 18 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms, and, among these, an aliphatic saturated hydrocarbon group having 1 to 18 carbon atoms is preferable.

R in the general formula (2) is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms, still more preferably an alkyl group having 1 to 8 carbon atoms and particularly preferably an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, an isobutyl group and a tert-butyl group, a methyl group, an ethyl group, a n-propyl group and a n-butyl group are preferable, and a n-butyl group is more preferable.

The lower limit value of the content of the (B) component is preferably 0.00005 mass %, more preferably 0.0001 mass % and particularly preferably 0.0002 mass % when the total mass of the composition for semiconductor processing is set to 100 mass %. On the other hand, the upper limit value of the content of the (B) component is preferably 1 mass %, more preferably 0.8 mass % and particularly preferably 0.6 mass % when the total mass of the composition for semiconductor processing is set to 100 mass %. When the content of the (B) component is within the above-described range, it is possible to exhibit favorable processing characteristics and, furthermore, to maintain favorable processing characteristics even after the composition is stored for a predetermined period.

1.3. Content Ratio Between (A) Component and (B) Component

When the content of the (A) component in the composition for semiconductor processing according to the present embodiment is indicated by M[mass %], and the content of the (B) content is indicated by M[mass %], the lower limit value of the value of M/Mis preferably 1.0×10, more preferably to 1.3×10, still more preferably 1.5×10and particularly preferably 5.0×10. The upper limit value of the value of M/Mis preferably 1.0×10, more preferably 7.0×10and particularly preferably 5.0×10.

In the composition for semiconductor processing according to the present embodiment, when the value of M/M, which is the content ratio between the (A) component and the (B) component, is within the above-described range, deterioration of the composition for semiconductor processing is suppressed, and the manufacturing yield of semiconductor elements can be improved. On the other hand, when the value of M/Mexceeds the above-described range, deterioration of the composition for semiconductor processing is likely to progress during the heating and use of the composition, and stable processing characteristics cannot be maintained, which is not preferable.

1.4 (C) Component

The composition for semiconductor processing according to the present embodiment contains (C) a compound having at least one functional group selected from the group consisting of an amino group and a salt thereof (excluding a compound having a carboxyl group and a nitrogen-containing heterocyclic compound). It is conceivable that, when the composition contains the (C) component, in the case of removing a resist film from a semiconductor substrate, it is possible to promote the dissolution of the resist film. In addition, it is conceivable that, in the case of cleaning an object to be processed after the end of CMP, it is possible to effectively remove a metal oxide film (for example, a CuO, CuO or Cu(OH) layer) or an organic residue (for example, a BTA layer) on the semiconductor substrate by etching. Furthermore, it is conceivable that, in the case of removing a residue after the dry etching step, it is possible to promote the dissolution of the residue and thereby improve removability.

The (C) component is preferably water-soluble. “Being water-soluble” in the present specification refers to the fact that the mass of a substance that dissolves in 100 g of water at 20° C. is 0.1 g or more. In addition, the (C) component preferably further has a hydroxyl group aside from at least one functional group selected from the group consisting of an amino group and a salt thereof.

Examples of the (C) component include primary amines such as monoethanolamine, monopropanolamine, monoisopropanolamine, methylamine, ethylamine, propylamine, butylamine, pentylamine and 1,3-propanediamine; secondary amines such as diethanolamine, dipropanolamine, diisopropanolamine, N-methylethanolamine, N-ethylethanolamine and N-((3-aminoethyl)ethanolamine; tertiary amines such as triethanolamine, tripropanolamine, triisopropanolamine, N-methyl-N,N-diethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, N,N-dibutylethanolamine, trimethylamine and triethylamine; and quaternary ammonium salts such as tetramethylammonium hydroxide. These (C) components may be used singly or two or more thereof may be used in combination.

Among these (C) components, from the viewpoint of a particularly high effect of removing a resist film on a semiconductor substrate, at least one selected from the group consisting of methanolamine, ethanolamine, isopropanolamine and diethylethanolamine is preferable, ethanolamine and isopropanolamine are more preferable, and monoethanolamine and monoisopropanolamine are particularly preferable.

The lower limit value of the content of the (C) component is preferably 0.01 mass %, more preferably 0.1 mass % and particularly preferably 0.5 mass % when the total mass of the composition for semiconductor processing is set to 100 mass %. On the other hand, the upper limit value of the content of the (C) component is preferably 10 mass %, more preferably 5 mass % and particularly preferably 3 mass % when the total mass of the composition for semiconductor processing is set to 100 mass %. When the content of the (C) component is within the above-described range, performance for removing a resist film or cleaning performance for removing a residue after the dry etching step becomes high, which is preferable.

1.5 (D) Component

The composition for semiconductor processing according to the present embodiment contains (D) a liquid medium as a main component. The (D) component can be selected as appropriate depending on the intended use of the processing agent such as the cleaning of an object to be processed, etching or the removal of a resist film.

As the (D) component, an aqueous medium containing water as a main component is preferable. Examples of such an aqueous medium include water, solvent mixtures of water and an alcohol and solvent mixtures containing water and an organic solvent that is compatible with water. Among these aqueous mediums, water or the solvent mixtures of water and an alcohol are preferably used, and water is more preferably used.

Examples of the organic solvent include well-known organic solvents that can be used in a semiconductor processing step such as polar solvents such as ketone-based solvents, ester-based solvents, ether-based solvents, amide-based solvents, glycol-based solvents and sulfur-containing compound-based solvents and hydrocarbon-based solvents.

Examples of the ketone-based solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methyl naphthyl ketone, isophorone and the like.

The ester-based solvents may be chain ester-based solvents or may be cyclic ester-based solvents. Examples of the chain ester-based solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, propyl-3-methoxypropionate and the like. In addition, examples of the cyclic ester-based solvents include lactones such as γ-butyrolactone, ethylene carbonate, propylene carbonate and the like.

Examples of the ether-based solvents include glycol ether-based solvents such as ethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol dibutyl ether; diisopentyl ether, diisobutyl ether, dioxane, tetrahydrofuran, anisole, perfluoro-2-butyltetrahydrofuran, perfluorotetrahydrofuran, 1,4-dioxane and the like.

Examples of the amide-based solvents include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone and the like.

Examples of the glycol-based solvents include ethylene glycol, diethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol and the like.